Phosphate esters of alkoxylated straight-chain primary alcohols



United States Patent 3,462,520 PHOSPHATE ESTERS 0F ALKOXYLATEDSTRAIGHT-CHAIN PRIMARY ALCOHOLS Louis J. Nehmsmann, Metuchen, and LeslieM. Schenck, Mountainside, N.J., assignors to GAF Corporation, New York,N.Y., a corporation of Delaware No Drawing. Filed Oct. 14, 1966, Ser.No. 586,627 Int. Cl. Clld 1/34; C07f 9/08 US. Cl. 260-950 7 ClaimsABSTRACT OF THE DISCLOSURE A surface active phosphate ester compositionselected from the class consisting of esters having the followingformulae:

and

This invention relates to a new class of phosphate esters of alkoxylatedalcohols having improved .physical characteristics and to the process ofpreparing the same.

Phosphate esters of anionic surfactants such as of ethoxylates ofalkylated phenols, ethoxylates of branched chain aliphatic alcohols, andethoxylates of linear primary alcohols of from 10 to carbon atoms arealso well known and methods for their preparation are disclosed invarious patents, such as USP 3,004,056, 3,004,057, 3,010,- 903,3,033,889 3,099,676, and 3,235,627. Although the phosphate estercompositions of the type prepared in accordance with the procedure givenin these patents display excellent properties as emulsifiers, wettingagents, dispersing agents, detergents, softening agents and the like,they show a wide variation in physical characteristics. The most notableis the difference in pour points of phosphate esters based onethoxylated alkyl phenols, ethoxylated long-chain primary alcoholscontaining at least 3 side chains, and ethoxylated linear aliphaticprimary alcohols.

The following tabulation shows the pour points of phosphate estersrepresentative of the foregoing type:

Phosphate ester of- Pour point in F.

Nonyl phenol+64% E.O 35 Nonyl phenol+54.5% E.O. 35 Tridecylalcohol-oxo+56.9% E.O 35 C -C linear .primary alcohol-{64.5% E.O. 75 C-C linear primary alcohol+68% E.O. 80 C -C linear primary alcohol+64%E.O. 75 C linear primary alcohol+57% E.O. 75 C linear primary alcohol+57Pr. 0 70 From the foregoing data, it is apparent the phosphate esterswhich constitute the chief articles of commerce, i.e., those derivedfrom nonionics containing from 54-68% ethylene oxide by weight, areliquid at ambient tempera- Patented Aug. 19, 1969 tures but tend tosolidify at lower temperatures unless they are prepared from nonionicsbased on alkylphenol and branch chain alcohol hydrophobes.Solidification below ambient, i.e., 70 F., temperatures present aproblem not only in storage but also in handling operations duringcooler weather when warehousing and storage temperatures are normallymaintained in the 50-60 F. range. Unfortunately, the products mostcommercially acceptable, due to their low pour points contributing totheir ease of storage and handling during cold weather, arenon-biodegradable, being based on the so-called biologically hardnonionics that use alkylphenol and branch chain alcohols as thehydrophobic portion of the molecule.

Although biodegradable phosphate ester surfactants With satisfactorychemical and use characteristics can be made for replacement ofalkylphenol and branched chain alcohol based products by phosphorylationof linear primary alcohol nonionics containing substantially theequivalent weight percentage of ethylene oxide, these phosphate estersare not commercially acceptable due to their physical characteristic ofbeing solids with pour points of approximately 70-80 F. Substitution ofethylene oxide by propylene oxide fails to lower the pour point, andimparts non-biodegradable properties to the ester molecule.

We have found that the foregoing disadvantages are readily overcome byfirst alkoxylating a straight-chain primary alcohol of from 10 to 20carbon atoms or a mixture of such alcohols with a controlled admixtureof ethylene and propylene oxides, followed by phosphorylation of themixed alkoxylate with phosphoric anhydride to yield biodegradablesurface-active compositions containing mixtures of primary and secondaryphosphate esters which have pour points ranging from about 45 F. toabout 60 F. The mixture of primary and secondary phosphate esters is notonly liquid and pourable at average room temperatures but alsobiodegradable and when subjected to the US. Cotton Soiled Cloth by theTerg-otometer test shows a final reflectance of around 30 as comparedwith 20-25 for the phosphate esters of the prior art.

In obtaining the phosphate esters having the above desirablecharacteristics, we first polyalkoxylate a primary saturated linearalcohol of from 8 to 20 carbon atoms, or a mixture of such alcohols,with an admixture consisting of 5 to 25% by weight of propylene oxideand from to by weight of ethylene oxide to yield a polyalkoxylatecontaining not less than 40% by weight and not more than 75 by weight ofthe mixed ethylene and propylene oxides in the final product. In otherwords, in the random polyalkoxylation of the alcohol, or mixturesthereof, we employ an admixture of ethylene oxide and propylene oxide inthe ratio of 5-25% by weight of propylene oxide to 7595% by weight ofethylene oxide wherein the polyalkoxy groupings (ethylene oxide andpropylene oxide) in the final product consist of not less than 40% to nomore than 75 by weight of final product. However, for maximum foam, pourpoint, cotton detergency, alkali stability, and biodegradability, Weprefer that the polyalkoxy groupings in the final product comprise fromabout 50% to 65% by weight of final product prior to phosphorylation.

Simplifying the foregoing ratios into moles, 1 mole of a primary linearsaturated alcohol of from 8 to 20 carbon atoms, or a mixture of suchalcohols, is condensed with about 1.5 to 20 moles of an admixturecontaining from 5 to 25 percent by weight of propylene oxide and from 75to 95 percent by weight of ethylene oxide in the presence of 0.05 to0.50 part by weight of caustic soda, based on the weight of the alcohol,as catalyst. The alkoxylation is carried out in a standard steelautoclave in which the alcohol or mixture of alcohols is charged,together with the caustic soda. Following the latter addition, theautoclave is purged with nitrogen, evacuated and then heated to atemperature ranging between 125 to 160 C., followed by the addition ofthe admixture of propylene and ethylene oxide at a pressure of from 15to 30 p.s.i.g. and a temperature of from 150 to 160 C. for a period oftime ranging from 1 to 12 hours until the alkoxylation is complete. Theautoclave is then cooled and its contents discharged. The resultingalkoxylate is then subjected to phosphorylation by the followingprocedure: Into any suitable reaction vessel equipped with agitator,thermometer and nitrogen inlet, there is added from about 2 to 4.5 molesof the alkoxylate as above obtained and one mole of P which is addedduring a period of about 1 hour, at which time the temperature risesfrom room to about 100 C. The reaction mixture is maintained at 100- 125for about 5 hours, cooled and discharged. The resulting mixture ofprimary and secondary esters is a clear liquid with a pour point rangingfrom 45 F. to about 60 F.

When employing P 0 as the phosphorylating agent, a mixture consisting offrom 25 to 60% by weight of monoester and from to 65% by weight ofdiester is obtained having the following formulas:

01-1 on RO(alkylene-O)n P O (monoester) and wherein R is at least onealkyl of from 8 to carbon atoms, and -(alkylene0) represents a randomdistribution of oxyethylene and oxypropylene groups in the ratio of from75%95% by weight of oxyethylene to 5%25% by weight of oxypropylene andwherein the said oxyethylene and oxypropylene groups comprise about 40%to about 75% by weight in the non-ionic molecule, -RO(alky1ene-O) Themixture of monoand di-esters obtained in accordance with the presentinvention is not only clear but also free of sludge during storage atambient temperatures and with a pour point of from 45 F. to about 60 R,which represents a pour point depression by about to 40 F. in comparisonto the monoand diesters of the prior art having the same cloud point indistilled water.

The primary monohydric straight chain linear alcohols and mixturesthereof, which are first alkoxylated, include (diester) l-octanol,l-nonanol, l-decanol, l-undecanol, l-dodecanol, l-tridecanol,l-tetradecanol, l-pentadecanol, 1- hexadecanol, l-heptadecanol,l-octadecanol, l-nonadecanol and l-eicosanol.

Although straight-chain primary alcohols containing from 8 to 20 carbonatoms, or admixtures of such alcohols respond to the foregoingalkoxylation and phosphorylation reaction conditions, when a mixture ofalcohols is employed, we prefer an admixture containing from 0 to 10percent of a C alcohol, 12 to 24 percent of a C alcohol, 25 to percentof a C alcohol, 12 to 24 percent of a C alcohol and from 0 to 10 percentof alcohols containing less than 11 carbon atoms and more than 15 carbonatoms, and alkoxylated with an admixture of ethoxylene and propyleneoxides containing from 85% to 95% by weight of ethoxylene oxide and from5% to 15% by weight of propylene oxide.

The following examples are illustrative of the present invention. It isto be understood that all parts and percentages referred to therein areby weight unless otherwise indicated:

EXAMPLE I There is charged into an autoclave 480 parts by weight of a C-C straight chain primary alcohol admixture representing 2.3 moles ofalcohol having the following composition: 15% C12, 31% C13 31% C14, and23% C and an average molecular weight of 209. There is then added 0.5part by weight of caustic soda as catalyst and the autoclave purged withnitrogen, evacuated, then heated to 150 C. Seven hundred and twentyparts by weight of 90/ 10% by weight mixture of ethylene oxide topropylene oxide (15.9 moles) are added at 15-30 p.s.i. and a temperatureof 150160 C. for 2 hours. Upon cooling, the autoclave was discharged toyield 1206 parts by weight of alkoxylate product. The resulting producthas a cloud point of 36 C. (1% solution in distilled water).

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet, 515 parts by weight (0.99 mole) of theabove alkoxylate. There is then added 52.5 parts by weight (0.37 mole)of P 0 at 15 to 115 C. over about one hour. The reaction mixture isheated at 100115 C. for five hours, cooled, and discharged. Theresulting ester is a clear liquid with a pour point of F. In alaboratory tergitometer test using 0.25% concentration in 200 ppm. waterof a built formulation containing 10% phosphate ester, 35% STPP (sodiumtri-poly hosphate), 5.0% Na SiO 49.0% Na SO and 1.0% carboxy methylcellulose (CMC), the final reflectance of a U.S. Testing swatch was30.0.

Ross-Miles Foam, 0.05% concentration at 25 C., 300 ppm. water, initiatedat 55 mnr; at 5 minutes.

EXAMPLE Ia This example shows the difference in physical properties andpour point when the alcohol of Example I is converted to the samecloudpoint nonionic with 100% ethylene oxide, then converted to thephosphate ester.

As a control, 480 parts by weight of the C1215 straight chain primaryalcohol admixture of Example I was ethoxylated to a 36 C. cloudpoint indistilled water using 680 parts of ethylene oxide.

A 500 gram aliquot of the above nonionic was converted to the phosphateester as in Example I using a ratio of 2.67 mole of nonionic per 1 moleof P 0 The resulting ester was a semi-solid at ambient temperature witha pour point of 76 F. In a laboratory tergiotometer test using 0.25%concentration in 200 ppm. water of a built formulation containing 1%phosphate ester, 35% sodium tri-poly phosphate (STPP), 5 .0% Na SiO49.0% Na SO and 1.0% carboxy methyl cellulose (CMC), the finalreflectance of a U.S. Testing swatch was 27.

Ross-Miles Foam, 0.05% concentration at 25 C., 300 ppm. water, initiatedat mm.; 50 at 5 minutes.

EXAMPLE II There is charged into an autoclave 420 parts by weight of a C-C straight chain primary alcohol representing 2.05 moles of alcoholcalculated as a 203 M.W. average and having the following composition:2% C 23% C 32% C13, 29% C14, 15% C There is then added 0.5 part byweight of caustic soda as catalyst and the autoclave purged withnitrogen, evacuated, then heated to 150 C. Five hundred and eighty partsby weight of /10% by weight mixture of ethylene oxide to propylene oxide(12.9 moles) were added at 15-30 p.s.i. and ISO-160 C. Upon cooling, theautoclave was discharged to yield 998 part by weight of product. Theresulting nonionic is cloudy at 25 C. 1% solution in distilled water.)

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet, 490 parts by weight (1.0 mole) of theabove alkoxylate. There is then added 52.5 parts by weight (0.37 mole)of P 0 at 15 to 115 C. over about one hour. The reaction mixture isheated at 115 C. for five hours, cooled, and discharged. The resultingester is a clear liquid with a pour point of 45 F. In a laboratorytergitometer test using 0.25 concentration in 200 ppm. water of a builtformulation containing 10% phosphate ester, 35% STPP, 5.0% Na SiO 49.0%Na SO and 1.0% CMC, the final reflectance of a U.S. Testing swatch was31.0.

5 Ross-Miles Foam, 0.05% concentration at 25 C., 300 p.p.m. water,initiated at 55 mm.; 50 at 5 minutes.

EXAMPLE III There is charged into an autoclave 433 parts by weight of aC3-C straight chain primary alcohol representing 2.07 moles of alcoholcalculated as a 209 M.W. average and having the following composition:15% C 3 1% C 31% C 23% C There is then added 0.5 part by weight ofcaustic soda as catalyst and the autoclave purged with nitrogen,evacuated, then heated to 150 C. Seven hundred and sixty-seven parts byweight of 91/ 9% by weight mixture of ethylene oxide to propylene oxide16.8 moles) were added at 15-30 p.s.i. and 150160 C. Upon cooling, theautoclave is discharged to yield 1195 parts by weight by product.

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet 575 parts by weight (1.0 mole) of theabove alkoxylate. There is then added 52.5 parts by weight (0.37 mole)of P at 15 to 115 C. over about one hour. The reaction mixture is heatedat 100-115 C. for five hours, cooled, and discharged. The resultingester is a clear liquid with a pour point of 55 F. In a laboratorytergitometer test using 0.25 concentration in 200 p.p.m. water of abuilt formulation containing phosphate ester, 35% STPP, 5.0% Na SiO49.0% Na SO and 1.0% CMC, the final reflectance of a US. Testing swatchwas 30.0.

Ross-Miles Foam, 0.05% concentration at 25 C., 300 p.p.m. water,initiated at 60 mm.; 55 at 5 minutes.

EXAMPLE 1V There is charged into an autoclave 455 parts by weight of a CC straight chain primary alcohol representing 2.34 moles of alcoholcalculated as a 195 M.W. average and having the following composition:0.5% C C 35% 13, C 14.5% C There is then added 0.5 part by weight ofcaustic soda as catalyst and the autoclave purged with nitrogen,evacuated, then heated to 15 0 C. Seven hundred and forty-five parts byweight of 90/ 10% by weight mixture of ethylene oxide to propylene oxide(16.4 moles) were added at 15-30 p.s.i. and 150- 160 C. Upon cooling,the autoclave is discharged to yield 1195 parts by weight of product.

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet 545 parts by weight (1.0 mole) of theabove alkoxylate. There 1s then added 52.5 parts by weight (0.37 mole)of P 0 at 15 to 115 C. over about one hour. The reaction mixture isheated at 100115 C. for five hours, cooled and discharged. The resultingester is a clear liquid with a pour point of 55 F. In a laboratorytergitometer test using 0.25% concentration in 200 p.p.m. water of abuilt formulation containing 10% phosphate ester, 35 STPP, 5.0% Na SiO49.0% Na SO and 1.0% CMC, the final reflectance of a US Testing swatchwas 31.0.

RossMiles Foam, 0.05 concentration at 25 C., 300 p.p.m. water, initiatedat 60 mm.; 50 at 5 minutes.

EXAMPLE V There is charged into an autoclave 390 parts by weight of anoctonoic straight chain primary alcohol representing 3.0 moles ofalcohol calculated as a 131 M.W. average and having the followingcomposition: 0.5% C 98% C and 15% C There is then added 0.5 part byweight of caustic soda as catalyst and the autoclave purged withnitrogen, evacuated, then heated to 150 C. Two hundred and sixty partsby weight of 95/5% by weight mixture of ethylene oxide to propyleneoxide (5.7 moles) were added at 15-30 p.s.i. and ISO-160 C. Uponcooling, the autoclave is discharged to yield 645 parts by weight ofproduct.

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet 215 parts by weight (1.0 mole) of theabove alkoxylate. There is then added 52.5 parts by weight (0.37 mole)of P 0 at 15 to 115 C. over about one hour. The reaction mixture isheated at 115 C. for five hours, cooled, and discharged. The resultingester is a clear liquid with a pour point of 47 F.

EXAMPLE VI There is charged into an autoclave 298 parts by weight of anarachidyl straight chain primary alcohol representing 1.0 mole ofalcohol calculated as a 298 M.W. average and having the followingcomposition: 0.5% C 99% C 0.5% C There is then added 0.5% part by weightof caustic soda as catalyst, and the autoclave purged with nitrogen,evacuated, then heated to 150 C. Upon cooling, the autoclave isdischarged to yield 1190 parts by weight of product. The resultingnonionic has a cloud point of 70 C. 1% solution in distilled water).

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet 478 parts by Weight (0.4 mole) of theabove alkoxylate. There is then added 21.4 parts by weight (0.15 mole)of P 0 at 15 to C. over about one hour. The reaction mixture is heatedat 100-115 C. for five hours, cooled, and discharged. The resultingester is a clear liquid with a pour point of 50 F.

EXAMPLE VII There is charged into an autoclave 214 parts by weight of amyristryl straight chain primary alcohol representing 1.0 mole ofalcohol calculated as a 214 M.W. average and having the followingcomposition: 1.0% C 98% C 1.0% C There is then added 0.5 part by weightof caustic soda as catalyst, and the autoclave purged with nitrogen,evacuated, then heated to C. Three hundred and twenty parts by weight of90/10% by weight mixture of ethylene oxide to propylene oxide (7.0moles) were added at 15-30 p.s.i. and 150160 C. Upon cooling, theautoclave is discharged to yield 530 parts by weight of product. Theresulting nonionic has a cloud point of 52 C. (1% solution in distilledwater).

There is charged to a one liter four-neck flask equipped with agitator,thermometer, and nitrogen inlet 530 parts by weight (1.0 mole) of theabove alkoylate. There is then added 35.5 parts by weight (0.25 mole) ofP 0 at 15 to 115 C. over about one hour. The reaction mixture is heatedat 100-115 C. for five hours, cooled, and discharged. The resultingester is a clear liquid with a pour point of 55 F. In a laboratorytergitometer test using 0.25 concentration in 200 p.p.m. water of abuilt formulation containing 10% phosphate ester, 35 STPP, 5.0% Na SiO49.0% Na SO and 1.0% CMC, the final reflectance of a US. Testing swatchwas 31.

Ross-Miles Foam, 0.05% concentration at 25 C., 300 p.p.m. water,initiated at 55 mm.; 50 to 5 minutes.

We claim:

1. A surface avtice phosphate ester composition selected from the classconsisting of esters having the following formulae:

wherein R represents a straight chain alkyl of from 8 to 20 carbon atomsand wherein the alkyleneoxy grouping, -(alkyleneO) represents a randomdistribution of oxyethylene and oxypropylene groups in the non-ionicmolecule RO-(alkylene0) in the ratio of from 5% to 25% by weight ofoxypropylene to 75%-95% by weight of oxyethylene and wherein the saidoxypropylene and oxyethylene groups comprise about 40% to 75% by weightof said non-ionic molecule.

2. A mixture of surface active phosphate esters selected from the classconsisting of esters having the following formulae:

wherein R represents a straight chain alkyl of from 8 to 20 carbon atomsand wherein the alkyleneoxy grouping, --(alkylene-O) represents a randomdistribution of oxyethylene and oxypropylene groups in the non-ionicmolecule RO(alkylene--O) in the ratio of from 5% to 25% by weight ofoxypropylene to 75%95% by weight of oxyethylene and wherein the saidoxypropylene and oxyethylene groups comprise about 40% to 75% by weightof said non-ionic molecule.

3. A surface active phosphate ester composition according to claim 1wherein R is a straight chain alkyl of eight carbon atoms.

4. A surface active phosphate ester composition ac- References CitedUNITED STATES PATENTS 10/1966 Nehmsmann et a1. 260-950 7/1968 Nehmsmannet al. 260950 JOSEPH P. BRUST, Primary Examiner ANTON H. SU'ITO,Assistant Examiner US. Cl. X.R.

" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,462 520 Dated August 19 1969 lnventofls) LOUIS J. NEHMSMANN ET AL It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 4, line 44, "1% phosphate ester" should read 107 phosphate esterColumn 6, line 42, "alkoylate" should. read alkoxylate NOV 1219]) EdwardM. Hatchet, Jr.

mm H. mm, JR. Awestlng O domissioner of Patentll

